Stabilized halogenated oils



3,008,833 STABILIZED HALOGENATED OILS Jack M. Bechtel, Chicago, and Frank E. Kuester, La Grange Park, Ill., and Earle Fritz, East Chicago, Ind., assignors to Swift & Company, Chicago, 111., a corporation of Illinois No Drawing. Filed July 1, 1957, Ser. No. 668,921

' Claims. (Cl. 99-163) This invention relates in general to the stabilization of halogenated glyeeride oils and, more particularly, to the inhibition or prevention of color, odor and flavor deterioration in halogenated glyceride oils.

Halogenated oils, specifically brominated oils such as brominated sesame oil, brominated apricot kernel oil, brominated corn oil, brominated soybean oil and other brominated oils of a similar nature, have been employed in the preparation of citrus-flavored beverages and have been suggested for use in the confectionery and baked foods industries where citrus-flavored oils are employed. Since citrus oils have a specific gravity of less than 1 and are insoluble in water, one of the most desirable means for suspending these flavoring oils in water is by combining the citrus oil with high density miscible liquids such as brominated oils. By this means it is possible to suspend the citrus oil-brominated oil mixtures in water and produce a cloudy citrus-flavored liquid which can then be further formulated into an attractive, typical citrus-flavored beverage. The brominated oils which have been employed in the past for this purpose possess a high specific gravity in the range about 1.2-1.3 and reputedly provide a good stable cloud in citrus-flavored beverages in which they are incorporated. Moreover, these brominated oils are said to enhance the stability of the oil-water emulsion and olfer no interference with the citrus flavor. I

While the brominated oils which have been used as weighting agents in citrus-flavored beverages and foodstuffs have been satisfactory insofar as providing cloud stability and high specific gravity to the materials to which they are added, these products do not always possess the 'most desirable color properties and often deteriorate with age, as evidenced by darkening in color and the development of unpleasant odors and flavors.

It is therefore an object of this invention to provide brominated oils having an increased resistance to deterioration and improved flavor and odor characteristics.

Another object is to provide a brominated oil of good color and bland flavor.

A fm'ther object of this invention is the provision of a method for stabilizing brominated oils against color, odor and/or flavor deterioration.

Additional objects, if not specifically set forth herein, be readily apparent to one skilled in the art from the detailed description which follows.

Generally, it is within the contemplation of the present invention to provide a brominated oil of increased shelf life, desirable color, and good suspending properties by the incorporation in the brominated oil of a stabilizing amount of an epoxy-containing fatty material. Brominated oils which may be treated in accordance with the present invention include, generally, animal, vegetable and marine glycerides which contain suflicient bromine to provide a specific gravity in the range desired. Glyceride oils containing fatty acid radicals having unsaturated bonds which may be reacted with bromine are desirable as the source of the brominated oils. In addition to the unsaturated higher aliphatic fatty acid glyceride esters, other materials such as unsaturated higher aliphatic alcohols and unsaturated higher aliphatic acid esters of mono. and dihydric alcohols may also be brominated to provide the high density oil. A wide range "Ice of specific gravity oils is possible because of the great variation in the degree of unsaturation contained in naturally occurring fatty materials. The following brominated oils with data on specific gravity value for each clearly illustrate the 'wide range of specific gravities which is possible.

Brominated oil: Specific gravity Lard oil 1.12-1.17 Olive oil 1.19-1.24 Corn nil 1.30-1.37 Sesame nil 1.27-1.34 Cottonseed oil 1.25-1.32 Soybean oil 1.35-1.40 Safllowcr seed oil 1.40-1.50 Apricot kernel oil 1.26-1.33 Methyl nleate 1.14-1.19

Of course, mixtures of these various brominated oils provide for intermediate specific gravities. Moreover, partially brominated oils such as partially brominated soybean oil also provide specific gravity variations.

The stabilizing agent which is incorporated in the brominated oil to provide desirable color properties may be characterized as a fatty material containing one or more oxirane groups in the molecule. Epoxidized fatty materials are particularly satisfactory for this purpose. Such epoxidized oils are epoxidized soybean oil, epoxidized cottonseed oil, epoxidized linseed oil, epoxidized rapeseed oil, epoxidized menhaden oil, epoxidized peanut oil, epoxidized lard oil, epoxidized tallow and epoxidized safllower oil may be employed as the stabilizing agent. Other epoxy-containing esters such as methyl epoxy stearate, ethyl epoxy stearate and triepoxy stearin are suitable as the oxiranecontaining component. These epoxy-containing fatty materials may be prepared from fatty acids and esters containing unsaturated bonds by procedures well known in the art, such as, for example, by the use of percarboxylic acids.

The amount of the epoxy-containing fatty material which provides the benefits of the present invention will vary both with the particular stabilizer employed. and also with the oil to be stabilized but includes from about .08% to 5% based on the weight of the brominated oil of the epoxy fatty material. While larger amounts may be used, there is no particular advantage to be gained from larger quantities since the increased stabilization benefits obtained are not commensurate with the excess added.

However, it is of course possible to add substantial quantities of the epoxy fatty material to the brominated oil and control the specific gravity of the mixture while also insuring that color deterioration is inhibited. The addition of the stabilizers of this invention to the high density oil can be accomplished readily, mere admixture being sufiicient to prepare a homogeneous product. It should be understood that the amount of a particular epoxidized fatty material to be added depends to some extent upon the oxirane content of the material being added. Thus, smaller amounts of polyepoxidized fatty materials such as epoxidized soybean oil are equal in effectiveness to greater quantities of such materials as methyl epoxy stearate. I

In order to demonstrate the stabilizing effect which the additives of this invention impart to brominated oils to which they are added, a mixture of 1 part soybean oil and 5 parts cottonseed oil, which had been brominated with bromine at low temperature, was treated with varying amounts of epoxidized fatty materials. The oil had a specific gravity of 1.33 and a desirable light color (11 on the PAC scale). This brominated oil was divided into several samples, one of which was retained as a control. To the other samples of this oil, varying amounts of epoxidized soybean oil (oxirane content 6.0%),

linseed oil (oxirane content 7.7%), and methyl epoxy 'stearate (oxirane content 3.6%) were added. All ofthe samples were subjected to accelerated ageing tests, i.e. holding at 150 F. for several days. The following table shows the color stabilization alforded by the epoxy-containing material:

Table I Oxirane FAG Color-Days at 150 F. Oxygen Content (Percent) 3 5 7 10 14 21 Control (fresh brominated oil) 0 11 19 21 21 21 21 21 Control+0.1% epoxidized soybean oil 0.006 11 17 21 21 21 21 21 Control+0. 5% epoxidized soybean oil 0.03 11 11 17 10 21 21 Control+1. 0% epoxidlzed soybean oil 0.00 11 11 13 13 13 15 21 Control+2. 0% epoxldlzed soybean oil 0.12 11 11 11 11 11 11 13 Gontrol+0. 08% epoxidlzed linseed oil 0.006 11 17 21 21 21 21 21 Oontrol+0.39% epoxidlzed see 0 0.03 11 11 15 17 10 21 21 Control+0.70% epoxldlzed linsee 0.06 11 11 13 13 13 17 21 Control+l. 58% epoxidlzed linseedo 0.12 11 11 11 11 11 11 13 Control-k0. 16% methyl epoxystearate- 0.006 11 17 21 21 21 21 21 Oontrol+0. 79% methyl epoxystearate 0.03 11 11 15 15 19 21 21 Control-H. 58% methyl epoxystearste 0.06 11 11 13 13 13 15 21 Control+3. 16% methyl epoxystearate 0.12 11 ll 11 11 11 11 13 The oxirane oxygen content, which is expressed in terms of percentage, is the product ofthe weight percent of the epoxidized material added and the oxirane oxygen content of that sample. It should be mentioned that after 21 days at 150 F. striking diflerences in color are apparent, but this difference is not noted in the color values reported above because of the poor sensivity of the PAC color standards in this range.

An additional advantage provided by the stabilizers of this invention lies in the fact that these materials also appear to provide a degree of bleaching or color improvement to darkened oils to which they are added.

This efiect is noted both with brominated oils which are relatively newly prepared, i.e., after about one month, and also with brominated oils which have undergone appreciable degradation, i.e., after standing for over a year. To demonstrate this color improvement or bleaching efiect, a sample of a brominated mixture of soybean and cottonseed oil stored at room temperature for about a month was divided into two parts, one part of which was retained as a control sample, the other part having 1% of the stabilizer based on the weight of brominated oil added thereto. The stabilizer in this case was epoxidized soybean oil having an oxirane content of about 6%. After standing for about a week, the two samples were compared on a Beckman spectrophotometer to compare colors. The transmission curves which were obtained showed that the sample containing the epoxidized soybean oil stabilizer allowed at least about 10% more transmission in the area of 400-600 millimicrons wave length than the sample containing no stabilizer. At 600 millimicrons, for example, the sample containing the stabilizer showed 80% transmission while that containing no stabilizer showed about 70% transmission.

A sample of brominated sesame oil while had been standing at room temperature for a period of about 18 months and which had become very dark in color and appeared to have undergone substantial degradation was divided into two parts. One part was retained as the control and about 1% based on the weight of the brominated oil of. epoxidized soybean oil having an oxirane content of about 6% was added to the other sample. The samples were held for about a week at room temperature to allow time for the -bleaching notion. The curves run on the spectrophotometer clearly illustrate the, remarkable degree of stabilization imparted by the epoxidized oil. In the wave length 520- 620 millimicrons the control sample showed very little transmission, reaching a at 620 of about 7.9%. The treated sample, on the other hand, showed an equivalent amount of transmission of 580 millimicrons and at 620 showed almost 20% transmission. Curves drawn up from this data show the striking advantage that the epoxidized material otters in bleaching or improving color of these brominated oils.

A further advantage in the use of the stabilizers of this invention with brominated oils lies in the resistance to heat deterioration of the oil provided by the stabilizers. For example, unstabilized brominated oils which have developed an unpleasant flavor or odor can be dcodorized to improve the flavor, provided a stabilizer is first added to the oil. In the absence of the stabilizer, an oil subjected to deodorization will darken in color, and flavor improvement is minimal. Any of the deodorization procedures known in the art such as steam deodorization and inert gas deodorization may be employed to improve flavor and odor characteristics of the oil. All of these procedures involve heating the oil however, thus accelerating degradation thereof. The stabilizers of this invention provide protection against this heat degradation.

It is, of course, to be understood that the stabilizing elfcct provided by the additives of this invention is noted in brominated oils prepared by any of the procedures well known in the art, and variations in methods of brominating oils are included within the scope of the invention.

Obviously, many modifications and variations of the invention as hereinbefore set forth may be made without departing from the spirit and scope thereof, and therefore only such limitations should be imposed as are indicated in the appended claims.

We claim:

1. In the production of brominated oils which tend to develop unpleasant flavors and odors the improvement comprising: adding to a brominated glyceride oil at least about .08% based on the weight of said oil of an epoxidized fatty acid ester and subjecting said oil containing said epoxidized ester to deodorization whereby to remove objectionable flavor and odor and retainthe desirable color of said oil.

2. A method of stabilizing a brominated glycerids oil against the development of undesirable odor and color characteristics which comprises: in said oil a stabilizing amormt of an epoxy-containing fatty ester.

3. A method of improving the color of a brominated vegetable oil and inhibiting the development of color degradation in said oil which comprises: adding to said brominated oil at least about 0.08% based on the weight of a1said brominated oil of an epoxy-containing fatty mate- -r1 4. A method of stabilizing brominated glyceride oil against the development of undesirable odor and color characteristics which comprises: adding to said oil more than about 0.08% of an epoxidized glyceride oil.

5. A method of improving the odor and flavor characteristics of brominated glyceride oil which comprises: adding to said oil a small amount of an epoxy-containing fatty material and subjecting said oil to deodorization.

6. A brominated oil containing at least about 08% of a stabilizer comprising an glyceride.

7. A brominated oil stabilized against color degradation and the development of undesirable odors which comprises: a brominated glyceride oil containing a stabilizing amount of an epoxy-containing fatty ester.

8. Brominated cottonseed oil containing a small amount, at least about .08% percent, based on the weight of the brominated oil, of epoxidized cottonseed oil.

9. A weighting agent adapted for use in the production of dispersions of water insoluble flavoring materials which comprises a mixture of brominated cottonseed oil and brominated soybean oil stabilized against color degradation by a stabilizing amount of epoxidized soybean oil.

10. A weighting agent adapted for use in the production of dispersions ofwater-insoluble flavoring materials which comprises: a brominated vegetable oil containing a color stabilizing amount of a material selected from the group consisting of epoxidized animal oils, epoxidized vegetable oils and epoxidized marine oils and mixtures thereof, the mixture containing at least 0.006% oxirane 5 oxygen.

References Cited in the file of this patent UNITED STATES PATENTS 2,272,484 Shelton Feb. 10, 1942 2,564,195 De Nie Aug. 14, 1951 2,731,431 Robitschek et a1 Jan. 17, 1956 

1. IN THE PRODUCTION OF BROMINATED OILS WHICH TEND TO DEVELOP UNPLEASANT FLAVORS AND ODORS THE IMPROVEMENT COMPRISING: ADDING TO A BROMINATED GLYCERIDE OIL AT LEAST ABOUT .08% BASED ON THE WEIGHT OF SAID OIL OF AN EXPOXDIZED FATTY ACID ESTER AND SUBJECTING SAID OIL CONTAINING SAID EPOXIDIZED ESTER TO DEODORIZATITION WHEREGY TO REMOVE OBJECTIONABLE FLAVOR AND ODOR AND RETAIN THE DESIRABLE COLOR OF SAID OIL. 